[go: up one dir, main page]

WO2015058187A1 - Composition d'électrolyte en polymère solide - Google Patents

Composition d'électrolyte en polymère solide Download PDF

Info

Publication number
WO2015058187A1
WO2015058187A1 PCT/US2014/061361 US2014061361W WO2015058187A1 WO 2015058187 A1 WO2015058187 A1 WO 2015058187A1 US 2014061361 W US2014061361 W US 2014061361W WO 2015058187 A1 WO2015058187 A1 WO 2015058187A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer electrolyte
electrolyte composition
composition according
ionically
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2014/061361
Other languages
English (en)
Inventor
Geoffrey W. Coates
Rachna KHURANA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cornell University
Original Assignee
Cornell University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cornell University filed Critical Cornell University
Priority to US15/030,173 priority Critical patent/US10490848B2/en
Publication of WO2015058187A1 publication Critical patent/WO2015058187A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention generally relates to polymer electrolyte compositions, to processes for the preparation of the compositions, and to articles comprising the
  • Rechargeable batteries such as lithium (Li)-ion batteries
  • Li-ion batteries are promising candidates for various applications, including, e.g., electric vehicle applications, due to their high energy density.
  • the safety of such batteries is limited due to the use of flammable liquid electrolytes.
  • the specific energy density of current state-of-the-art Li- ion batteries is below the U.S. Department of Energy Vehicle Technologies Program's long- term target for secondary batteries.
  • Replacing flammable electrolytes and enhancing the energy density of Li -based battery technologies are at the forefront of research in both academia and industry.
  • Solid polymer electrolytes are an alternative to liquid electrolytes due to their non-volatility, low toxicity, and high energy density.
  • SPE's can be useful in, e.g., Li- metal based batteries and related electrochemical energy storage devices that require high ionic conductivity at ambient temperature (> 10—4 S/cm at 25 °C) and suppression of lithium dendrite growth. Such dendrite growth can occur in other batteries, which can cause short circuiting/over-heating/thermal run-away.
  • a rechargeable Li-metal based battery is considered to a promising technology for energy storage due to its high storage capacity, due to the use of lithium (Li) metal, instead of lithiated graphite.
  • Li lithium
  • its use with liquid electrolytes is currently limited by the formation of irregular Li electrodeposits (dendrites) during repeated charge-discharge cycles, which often lead to short circuit causing over-heating and thermal run-away.
  • SPEs solid polymer electrolytes
  • G' > 6 GPa high shear modulus
  • the present invention satisfies the need for an improved polymer electrolyte compositions, and for articles (e.g., batteries) comprising the same.
  • the present invention may address one or more of the problems and deficiencies of the art discussed above.
  • embodiments disclosed herein provide a number of advantages over the current state of the art. These advantages may include, without limitation, providing an improved polymer electrolyte composition that allows for improved battery operation (e.g., due to improved dendrite growth resistance).
  • the invention provides a polymer electrolyte composition
  • a hard polymer segment having:
  • T g glass transition temperature
  • an ionically-conducting segment having a molecular weight of 800 to 10,000 g/mol;
  • a salt comprising an element M, wherein M is selected from an alkali metal, an alkaline earth metal, zinc, and aluminum,
  • the hard polymer segment is covalently bound to the ionically-conducting segment, and wherein said polymer electrolyte composition has an ionic conductivity for an M ion greater than or equal to 1 x 10 - " 8 S/cm at 25 °C.
  • the invention provides an electrochemical cell comprising the polymer electrolyte composition as described above with reference to the first aspect of the invention.
  • the invention provides an energy storage device (e.g., a battery), comprising a plurality of electrochemical cells, wherein at least one of the plurality of electrochemical cells is an electrochemical cell according to the second aspect of the invention, as described above.
  • an energy storage device e.g., a battery
  • the invention provides a method for the preparation of the polymer electrolyte composition according to the first aspect of the invention, and, accordingly, for methods of preparing articles comprising the polymer electrolyte
  • composition comprising: co-polymerizing a mixture comprising a compound comprising the hard polymer segment or a precursor thereof and a compound comprising the ionically-conducting segment or a precursor thereof in the presence of Grubbs second-generation catalyst, the salt, and solvent; and
  • FIG. 1 depicts a plot of DC ionic conductivity as a function of temperature for
  • PEOX polymer electrolyte composition embodiments having different weight percent of PEG275 plasticizer. All films had [COE]:[l] ratio of 15: 1 and [EO]:[Li] composition of 18: 1. The conductivity of a PEO 900 kDa sample with [EO]:[Li] ratio of 18: 1 is also shown for comparison purposes.
  • FIGS. 2 A and 2B provide dendrite test results for polymer electrolyte composition embodiments.
  • FIG. 2 A provides galvanostatic cycling test data showing Q as a function of current density at 90 °C for ( 70 PEOX O . 34 )( 34 PE O . 35 )( 5 PEG 0 . 3I ) polymer electrolyte ( ⁇ ) and PEO 900 kDa ( ⁇ ). The cells were cycled at constant current density with each half cycle of 3 h until a short circuit was observed.
  • FIG. 2B provides galvanostatic polarization test data, namely, a plot of short circuit time rious 70
  • va PEOX polymer electrolyte composition embodiments having different weight percent (wt%) of the plasticizer (PEG275).
  • wt% weight percent of the plasticizer
  • the invention provides a polymer electrolyte composition
  • a hard polymer segment having:
  • T g glass transition temperature
  • the hard polymer segment which has at least one of a glass transition temperature (T g ) greater than or equal to 110 °C and a melting temperature (T m ) greater than 110 °C, provides mechanical integrity to the polymer film.
  • T g glass transition temperature
  • T m melting temperature
  • the hard polymer segment comprises a Ci 5 to C 80 alkyl group (i.e., an alkyl group having 15 to 80 carbon atoms, e.g., 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 carbon atoms), including any and all ranges and subranges therein (e.g., C30-C50, etc.).
  • a Ci 5 to C 80 alkyl group i.e., an alkyl group having 15 to 80 carbon atoms, e.g., 15, 16, 17, 18, 19, 20, 21, 22,
  • the hard polymer segment represents only a segment of the inventive polymer electrolyte composition.
  • the polymer electrolyte composition typically comprises a plurality of hard polymer segments.
  • the entire PE backbone which comprises PE units from both the independent cyclooctene COE and cyclooctene residue of PEOXl
  • the entire PE backbone represents PE units from both the independent cyclooctene COE and cyclooctene residue of PEOXl
  • represents a hard polymer portion having many times more carbon units than the hard polymer segment described herein, e.g., in some embodiments, -10,000 carbons
  • the hard polymer segment is a C15 to C 80 alkyl group adjoining two ionically conducting segments.
  • the hard polymer segment comprises units of a semicrystalline polymer selected from polyethylene (PE), polyethylene terephthalate (PET), polynorbornene, polydicyclopentadiene, poly(4-methyl-l-pentene), polytetrafluoroethylene (PTFE) and isotactic or syndiotactic polypropylene (PP).
  • the hard polymer segment comprises polyethylene.
  • the hard polymer segment comprises 10 to 40 repeating units of polyethylene, i.e., the hard polymer segment comprises a structural unit of the formula
  • n" is a number from 10 to 40 (e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40), including any and all ranges and subranges therein.
  • the hard polymer segment has a glass transition temperature (T g ) from 110 to 400 °C, or a melting temperature (T m ) from 110 to 400 °C (e.g., 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, or 400 °C), including any and all ranges therein.
  • T g glass transition temperature
  • T m melting temperature
  • the hard polymer segment has a glass transition temperature (T g ) from 110 to 170 °C, or a melting temperature (T m ) from 110 to 170 °C.
  • the ionically-conducting segment comprises one or more structural units that show ionic conductivity when ionic salts are dissolved in them.
  • the ionically-conducting segment is covalently bonded to the hard polymer segment.
  • the ionically-conducting segment has a molecular weight of 800 to 10,000 g/mol (e.g., 800, 900, 1000, 1250, 1500, 1750, 2000, 2250, 2500, 2750, 3000, 3250, 3500, 3750, 4000, 4250, 4500, 4750, 5000, 5250, 5500, 5750, 6000, 6250, 6500, 6750, 7000, 7250, 7500, 7750, 8000, 8250, 8500, 8750, 9000, 9250, 9500, 9750 or 10000 g/mol), including any and all ranges and subranges therein.
  • the ionically- conducting segment has a molecular weight of 1,750 to 8,000 g/mol. In particular embodiments, the ionically-conducting segment has a molecular weight of 2,000 to 6,000 g/mol. In some embodiments, the ionically-conducting segment has a molecular weight of 2,500 to 4,000 g/mol.
  • the ionically-conducting segment contributes to the conductivity of the polymer electrolyte composition, which has an ionic conductivity for an M ion greater than or equal to 1 x 10 "8 S/cm at 25 °C.
  • the ionically-conducting segment comprises polyethylene oxide (PEO). In some embodiments, the ionically-conducting segment comprises 30 to 140 repeating polyethylene oxide units, i.e., the ionically-conducting segment comprises a structural unit of the formula
  • n * is a number from 30 to 140 (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123
  • the ionically-conducting segment further comprises a structural unit of formula -(CH 2 )8-.
  • the ionically-conducting segment additionally comprises a benzene ring.
  • the ionically-conducting segment comprises a structural unit having the formula:
  • a represents a number from 30 to 140 (e.g., 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 40
  • the polymer framework of the polymer electrolyte composition is crosslinked.
  • the polymer framework is non- crosslinked (e.g., block copolymers, multiblock copolymers, graft copolymers, etc.).
  • the crystallization of the ionically conducting segment is suppressed by cross-linking the ionically conducting component.
  • the normally semicrystalline ion conducting material is made substantially amorphous via covalent or physical crosslinking.
  • the ionically-conducting segment comprises a residue from a precursor compound of the formula (I):
  • Embodiments of the inventive polymer electrolyte composition that comprise residues of compounds that begin and end with cycloalkylene groups (as in the case of embodiments comprising a residue from a precursor compound of formula (I)), may be crosslinked. This is because compounds of formula (I) can serve as crosslinkers during polymerization.
  • the inventive polymer electrolyte composition comprises a residue of a compound having a cycloalkylene groups at only one end of the compound. Such embodiments are less conducive to cross-linking.
  • the salt comprises an element M, wherein M is selected from an alkali metal, an alkaline earth metal, zinc (Zn), and aluminum (Al).
  • M is selected from an alkali metal and an alkaline earth metal.
  • M is selected from lithium (Li), sodium (Na), and potassium (K).
  • M is lithium.
  • M is sodium.
  • the salt is a lithium salt. In some embodiments, the salt is a binary lithium salt.
  • the salt is selected from of lithium
  • LiTFSI bis(trifluoromethanesulfonyl)imide
  • LiPF 6 lithium hexafluorophosphate
  • LiCF 3 S0 3 lithium trifluoromethanesulfonate
  • LiCIO 4 lithium perchlorate
  • LiAsF 6 lithium hexafluoroarsenate
  • LiN(CF 3 80 2 ) 2 bis(trifluoromethanesulfonimide)
  • LiN(CF 3 80 2 ) 2 lithium bis(perfluoroethylsulfonylimide) (LiN(C 2 F 5 S0 2 ) 2 ), lithium thiocyanate (LiSCN), lithium dicyanamide (LiN(CN) 2 ), lithium tris (trifluoromethanesulphonyl)methyl (LiC(CF 3 S0 2 ) 3 ), lithium bisoxalatoborate (LiB(C 2 0 4 ) 2 ), lithium oxalatoborates, lithium bis(chelato)borate, lithium alkyl fluorophosphates,
  • LiPF 3 (C 2 Fs) 3 LiPF 3 (CF 3 ) 3
  • the salt is LiTFSI.
  • the inventive polymer electrolyte composition may optionally include a plasticizer, which may improve ionic conductivity and/or support higher charge/discharge rates.
  • the plasticizer has a molecular weight of less than 2000 g/mol.
  • the plasticizer has a molecular weight of 100 to 2000 g/mol (e.g., 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, or 2000 g/mol), including any and all ranges and subranges therein (e.g., 100 to 1000 g/mol. , 200 to 500 g/mol, etc.)
  • the plasticizer comprises polyethylene glycol dimethyl ether (PEG). In a particular embodiment, the plasticizer comprises PEG of 250 molecular weight.
  • the inventive polymer electrolyte composition has an ionic conductivity for an M ion (i.e., an alkali metal ion, an alkaline earth metal ion, a zinc ion, or an aluminum ion) of
  • the inventive polymer electrolyte composition has an ionic conductivity for an M ion of greater than or equal to 1 x 10 "7 , 5 x 10 "7 , 1 x 10 "6 , 2 x 10 "6 , 4 x 10 "6 , 6 x 10 "6 , 8 x 10 "6 , 9 x 10 "6 , 1 x 10 "5 , 2 x 10 "5 , 3 x 10 "5 , 4 x 10 "5 , 5 x 10 "5 , 6 x 10 “5 , 7 x 10 "5 , 8 x 10 “5 , 9 x 10 “5 , 1 x 10 "4 , or 2 x 10 "4 S/cm at 25 °C.
  • the polymer electrolyte composition has an ionic conductivity for an M ion between, e.g., 1 x 10 "5 and 2 x 10 "4 S/cm at 25 °C, including any and all ranges and subranges therein.
  • the polymer electrolyte composition has a dendrite growth resistance (C d ) value greater than or equal to 25 C/cm at current density (J) value of 0.26 mA/cm and 90 °C.
  • Cd values for the galvanostatic cycling tests are calculated using the following equation:
  • C d t J
  • J the current density value measured in A/cm
  • C d the dendrite growth (e.g., lithium dendrite growth) resistance measured in C/cm 2 .
  • the polymer electrolyte composition has a dendrite growth resistance (C d ) value of greater than or equal to 25, 50, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, or 1200 C/cm 2 at current density (J) value of 0.26 mA/cm 2 and 90 °C.
  • C d dendrite growth resistance
  • the inventive polymer electrolyte composition is free of (i.e., does not include) a flammable organic solvent.
  • the total ionically-conducting material in the polymer electrolyte composition is significant enough to provide continuous pathways through the bulk material.
  • the total ionically-conducting material i.e., the sum of ionically- conducting segments
  • makes up 30% to 85% of the volume of the polymer electrolyte composition e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85%, including any and all ranges and subranges therein.
  • the total of hard polymer segments in the polymer electrolyte composition makes up 15 to 70% of the volume of the polymer electrolyte composition (e.g., 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70%), including any and all ranges and subranges therein.
  • the invention provides an electrochemical cell comprising the polymer electrolyte composition as described above with reference to the first aspect of the invention.
  • the invention provides an energy storage device (e.g., a battery), comprising a plurality of electrochemical cells, wherein at least one of the plurality of electrochemical cells is an electrochemical cell according to the second aspect of the invention, as described above.
  • an energy storage device e.g., a battery
  • the invention provides a method for the preparation of the polymer electrolyte composition according to the first aspect of the invention, and, accordingly, for methods of preparing articles comprising the polymer electrolyte
  • composition comprising: co-polymerizing a mixture comprising a compound comprising the hard polymer segment or a precursor thereof and a compound comprising the ionically-conducting segment or a precursor thereof in the presence of Grubbs second-generation or third generation catalyst, the salt, and solvent; and evaporating the solvent to obtain a polymer film.
  • the method for the preparation of the polymer electrolyte composition additionally comprises solid state hydrogenation reaction of the polymer film in the presence of a lithium salt.
  • the inventive method comprises: co-polymerizing a mixture comprising a cycloalkylene compound and a compound comprising the ionically-conducting segment or a precursor thereof in the presence of Grubbs second-generation catalyst, the salt, and solvent; evaporating the solvent to obtain a polymer film; and
  • the solvent is tetrahydrofuran (THF).
  • the cycloalkylene compound is cyclooctene.
  • the inventive polymer electrolyte composition is prepared by a method comprising at least one of: 1) Growth of a conducting polymer phase off a 'hard' backbone, with optional coupling of the chain ends to create a crosslinked polymer; 2) Growth of a 'hard' polymer phase off a conducting polymer backbone, with optional coupling of the chain ends to create a crosslinked polymer; 3) Reacting a
  • multifunctional 'hard' polymer with a multi-functional conducting phase to create a crosslinked polymer 4) Polymerization of a conducting macromonomer with another monomer that creates a 'hard' polymer backbone; 5) Polymerization of a 'hard'
  • Crabtree's catalyst [(COD)Ir(py)(PCy 3 )]PF 6 were purchased from Sigma-Aldrich and used as received.
  • Dibromo-p- xylene (97%>) was purchased from Alfa Aesar and used as received.
  • tetrahydrofuran was purchased from Fischer Scientific and dried over an alumina column and degassed by three freeze pump thaw cycles before use. Chloroform was dried over P 2 0 5 and distilled prior to use. Hydrogen (99.99%) was purchased from Airgas. CDCI 3 was purchased from Cambridge Isotope Laboratories (CIL) and used as received.
  • the SPE is cross-linked with PEO segments and contains a polyethylene
  • Poly(ethylene oxide) Crosslinker (PEOX); 1 was readily synthesized as described above from inexpensive starting materials in excellent yields.
  • Cyclooctene (COE) was copolymerized with 1 in the presence of Grubbs' second- generation catalyst (G2 catalyst) in THF in a fluoropolymer-lined dish. After slow evaporation of the solvent at 50 °C, thin translucent films were obtained. Upon hydrogenation of these unsaturated films catalyzed by the iridium catalyst trapped within the amorphous crosslinked matrix, the mechanical strength of membranes greatly improved, and they were further examined by electrochemical tests.
  • SPE embodiments were designed to include controlled fractions of free methoxy-terminated polyethylene glycol (PEG) oligomers as plasticizers to assess their effect on conductivity and mechanical properties of the membranes.
  • PEG polyethylene glycol
  • a variety of polymer electrolyte samples were prepared by varying the crosslinker length, [COE]:[l] ratio, and weight percentage (wt%) of the plasticizer.
  • EO ethylene oxide
  • compositions and thermal properties of the SPE embodiments are summarized below in Table 1, where nomenclature corresponds to that described above before the synthetic Schemes; each component in the SPE is given a symbol (e.g. PEOX for the PEO crosslinker), the number of repeat units for each of the components are shown in the superscripts, and the mole fraction of the units in the SPE is given in the subscripts.
  • PEOX for the PEO crosslinker
  • PEOX polymer electrolytes had the smallest polyethylene (PE) crystallites in the network (lowest T m ), which could be explained by the relatively higher cross-linking density in these SPEs that inhibited the PE crystallization in the network. Also, for polymer electrolytes having the same crosslinker length (e.g. entries 1-3), higher [COE]:[l] ratios yielded materials with better mechanical integrity.
  • [COE]:[l] ratio e.g. comparison of ionic conductivities of 76 PEOX electrolytes: entries 4, 5, and
  • the surprisingly high ionic conductivity of the 76 PEOX electrolytes may be a direct consequence of the low T g of these SPEs, allowing enhanced segmental motion of PEO in the amorphous domains thus facilitating lithium-ion conduction.
  • ( 76 PEOX 0 .66)( 18 PE 0 .34) exhibited maximum ionic conductivity (3.1 x 10 S/cm at 25 °C).
  • Galvanostatic lithium plate/strip electrochemical cycling measurements were performed in symmetric Li/SPE/Li cell to quantify the effect of the inventive SPE embodiments on the lifetime of lithium-metal based batteries. Measurements were performed at variable current densities, J, using a three hour lithium plating followed by a three hour lithium stripping routine designed to ensure that in the event of unstable electrodeposition, sufficient quantities of lithium is transported during each cycle to bridge the inter-electrode space and short-circuit the cell.
  • the SPE's resistance to dendrite growth is here quantified in terms of total charge passed, C d , at the time of cell failure by dendrite-induced short-circuits.
  • FIG. 2A reports C d values as a function of current density for a high molar mass PEO standard (M n 900 kDa) and ( 70 PEOX 0 .34)( 34 PE 0 .35)( 5 PEGo.3i).
  • the PE-PEO cross-linked SPE embodiment displayed significantly higher C d values than observed for PEO ( n 900 kDa) sample at all the measured current density values. Notably, it displayed a C d value of 1790 C/cm that is more than an order of magnitude greater than reported for PS- ⁇ - ⁇ block copolymers
  • Dendrite resistance of selected SPEs was also examined using more conventional, but much harsher galvanostatic polarization conditions.
  • the voltage response in a symmetric Li/SPE/Li cell is studied during continuous one direction plating at a prescribed current density.
  • the Li/SPE/Li symmetric cells were polarized at current densities in the range 0.26-1.0 mA/cm at 90 °C until the voltage drop was observed.
  • Cells galvanostatically polarized at current densities of less than or equal to 0.26 mA/cm were able to plate the entire Li electrode without short circuit; in these cases, divergence of the potential halted testing.
  • FIG. 2B shows the variation of the measured cell short circuit time
  • a method or device that "comprises”, “has”, “includes” or “contains” one or more steps or elements possesses those one or more steps or elements, but is not limited to possessing only those one or more steps or elements.
  • a step of a method or an element of a device that "comprises”, “has”, “includes” or “contains” one or more features possesses those one or more features, but is not limited to possessing only those one or more features.
  • a device or structure that is configured in a certain way is configured in at least that way, but may also be configured in ways that are not listed.
  • each range is intended to be a shorthand format for presenting information, where the range is understood to encompass each discrete point within the range as if the same were fully set forth herein.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne un composition d'électrolyte en polymère comprenant un segment de polymère dur en liaison covalente avec un segment à conduction ionique, et un sel qui comprend un élément M choisi parmi un métal alcalin, un métal alcalino-terreux, du zinc et de l'aluminium. Le segment de polymère dur présente une température de transition vitreuse (Tg) supérieure ou égale à 110 °C, ou une température de fusion (Tm) supérieure à 110 °C. Le segment à conduction ionique présente un poids moléculaire de 800 à 10000 g/mol. La composition d'électrolyte en polymère présente une conductivité ionique pour un ion M supérieure ou égale à 1 x 10-8 S/cm at 25 °C. Des procédés de préparation de la composition d'électrolyte en polymère sont également décrits, ainsi que des articles (par ex. des cellules électrochimiques et des dispositifs de stockage d'énergie) qui contiennent la composition d'électrolyte en polymère.
PCT/US2014/061361 2013-10-18 2014-10-20 Composition d'électrolyte en polymère solide Ceased WO2015058187A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/030,173 US10490848B2 (en) 2013-10-18 2014-10-20 Solid polymer electrolyte composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361892524P 2013-10-18 2013-10-18
US61/892,524 2013-10-18

Publications (1)

Publication Number Publication Date
WO2015058187A1 true WO2015058187A1 (fr) 2015-04-23

Family

ID=52828788

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/061361 Ceased WO2015058187A1 (fr) 2013-10-18 2014-10-20 Composition d'électrolyte en polymère solide

Country Status (2)

Country Link
US (1) US10490848B2 (fr)
WO (1) WO2015058187A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018528567A (ja) * 2015-07-09 2018-09-27 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． 固体ポリマー電解質

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102682124B1 (ko) * 2018-11-30 2024-07-08 삼성전자주식회사 고분자 화합물, 이를 포함하는 고체 전해질막, 및 상기 고체 전해질막을 포함하는 리튬공기전지
CN117543076B (zh) * 2024-01-10 2024-03-15 广东工业大学 一种氧杂加成聚醚酯基全固态聚合物电解质及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07109321A (ja) * 1993-08-18 1995-04-25 Shin Etsu Chem Co Ltd 複合固体電解質
US20100255383A1 (en) * 2009-02-27 2010-10-07 University Of Maryland, College Park Polymer Solid Electrolyte for Flexible Batteries

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3394172B2 (ja) 1997-12-09 2003-04-07 シャープ株式会社 電 池
CN1133685C (zh) 1999-07-09 2004-01-07 中国科学院化学研究所 一种聚合物固体电解质及其制备方法和用途
KR100419864B1 (ko) * 2001-11-15 2004-03-04 한국화학연구원 신규 가교제와 이를 함유하는 가교형 고체 고분자 전해질
CA2537721A1 (fr) 2003-09-05 2005-03-24 University Of Massachusetts Capsules polymeres amphiphiles et procedes associes d'assemblage interfacial
KR100746347B1 (ko) 2006-01-25 2007-08-03 한국과학기술원 다공성 매트릭스를 포함하는 고체 고분자 전해질 및 이를 이용한 리튬-고분자 이차전지
WO2009079757A1 (fr) 2007-12-21 2009-07-02 Bathium Canada Inc. Électrolyte pour batteries lithium-polymère
US9017882B2 (en) 2008-11-07 2015-04-28 Seeo, Inc. Electrodes with solid polymer electrolytes and reduced porosity
FR2963481A1 (fr) 2010-07-27 2012-02-03 Commissariat Energie Atomique Membrane minerale a electrolyte pour dispositifs electrochimiques, et dispositifs electrochimiques la comprenant.
US8722254B2 (en) * 2011-05-09 2014-05-13 Washington State University Research Foundation Flexible solid state conductors including polymer mixed with protein
CN103765661B (zh) 2011-09-02 2016-06-22 西奥公司 微球复合电解质
CN102496736A (zh) 2011-12-27 2012-06-13 瑞声新能源发展（常州）有限公司 锂-硫二次电池用全固态聚合物电解质及其制备方法
KR102034719B1 (ko) 2012-12-21 2019-10-22 삼성전자주식회사 리튬공기전지용 보호음극 및 이를 포함한 리튬공기전지

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07109321A (ja) * 1993-08-18 1995-04-25 Shin Etsu Chem Co Ltd 複合固体電解質
US20100255383A1 (en) * 2009-02-27 2010-10-07 University Of Maryland, College Park Polymer Solid Electrolyte for Flexible Batteries

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GUILHERME, L. A. ET AL.: "Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes", ELECTROCHIMICA ACTA, vol. 53, no. 4, 7 April 2007 (2007-04-07), pages 1503 - 1511 *
GUREVITCH, INNA ET AL.: "Nanocomposites of Titanium Dioxide and Polystyrene- Poly(ethylene oxide) Block Copolymer as Solid-State Electrolytes for Lithium Metal Batteries", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 160, no. 9, 23 July 2013 (2013-07-23), pages A1611 - A1617 *
JANNASCH, PATRIC: "Ionic conductivity in physical networks of polyethylene- polyether-polyethylene triblock copolymers", CHEMISTRY OF MATERIALS, vol. 14, no. 6, 2002, pages 2718 - 2724 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018528567A (ja) * 2015-07-09 2018-09-27 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． 固体ポリマー電解質

Also Published As

Publication number Publication date
US10490848B2 (en) 2019-11-26
US20160276706A1 (en) 2016-09-22

Similar Documents

Publication Publication Date Title
Hamsan et al. NH4NO3 as charge carrier contributor in glycerolized potato starch-methyl cellulose blend-based polymer electrolyte and the application in electrochemical double-layer capacitor
Zhu et al. Poly (ionic liquid)@ PEGMA block polymer initiated microphase separation architecture in poly (ethylene oxide)-based solid-state polymer electrolyte for flexible and self-healing lithium batteries
CN107086324B (zh) 有机电解液和包含该有机电解液的锂电池
CN104466246B (zh) 用于锂电池电解质的添加剂、有机电解质溶液和锂电池
Yamada et al. Pyrrolidinium-based organic ionic plastic crystals: Relationship between side chain length and properties
EP3312919B1 (fr) Électrode positive pour batterie secondaire métallique et batterie secondaire métallique, comprenant celle-ci
US20180226679A1 (en) Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries
Gao et al. A self-healing poly (ionic liquid) block copolymer electrolyte enabled by synergetic dual ion-dipole interactions
Zhou et al. Star-shaped multi-arm polymeric ionic liquid based on tetraalkylammonium cation as high performance gel electrolyte for lithium metal batteries
KR101222381B1 (ko) 축전 디바이스
KR20170040175A (ko) 복합체, 그 제조방법, 이를 포함하는 전해질 및 리튬이차전지
Tseng et al. Lithium battery enhanced by the combination of in-situ generated poly (ionic liquid) systems and TiO2 nanoparticles
Le Mong et al. Self-healable, super Li-ion conductive, and flexible quasi-solid electrolyte for long-term safe lithium sulfur batteries
CN113265055B (zh) 梳状聚合物
US10490848B2 (en) Solid polymer electrolyte composition
US11876176B2 (en) Copolymer having functional group as substituent at chain-end, method for preparing electrolyte membrane for secondary battery including the same, and electrolyte membrane for secondary battery including the same
US12095032B2 (en) Solid polymer electrolyte including comb polymer containing polypentafluorostyrene grafted with solvating polymeric side chain
CN106415912B (zh) 用于电化学装置的添加剂、及包含其的电解质、电极及电化学装置
Vöge et al. Synthesis and properties of aromatic polyethers containing poly (ethylene oxide) side chains as polymer electrolytes for lithium ion batteries
Fu et al. Effects of molecular complexation on phase equilibria in mixtures of urea/polyethylene glycol derivatives and electrochemical performance of urethane based polymer electrolyte membranes for solid-state lithium ion battery
CN111019036B (zh) 一种用于柔性锂电池的纳米级高聚物电解质的制备方法
US20190312305A1 (en) Polymer, electrolyte including the same, and lithium battery including the polymer
KR102366929B1 (ko) 폴리(아릴렌에테르술폰)에 폴리(에틸렌글리콜)이 이중으로 그라프트된 공중합체, 이를 포함하는 리튬 이차전지용 고분자 전해질막 및 이의 제조 방법
US20240120537A1 (en) Composition
Lin et al. High-Voltage-Resistant Highly Stable Solid Polymer Electrolyte via In Situ Integrated Construction with Fast Ion Migration

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14853872

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15030173

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 14853872

Country of ref document: EP

Kind code of ref document: A1